Phosphorus-containing resins and the method of preparing the same



C1 2...... lack. s ings Patented Oct. 23, 1951 PHOSPHORUS-CONTATNING RESINS AND THE METHOD OF PREPARING THE SAME Arthur Dock Fon Toy, Chicago, Ill., assignor to Victor Chemical Works No Drawing. Application November 1, 1947, Serial No. 783,630

Claims. 1

This invention relates to organic phosphorus containing resins and more particularly to con: densation products of phosphorus dihalide compounds with chlorinated aromatic dihydroxy compounds in which the hydroxy radicals are on non-adjacent carbon atoms.

This application is a continuation-in-part of my copending application Serial No. 516,713, filed January 1, 1944, now U. S. Patent 2,435,252, dated February 3, 1948. v

I have discovered that; organic phosphorus dihalide compounds will condense with chlorinated dihydroxy aromatic compounds wherein the hydroxy radicals are on non-adjacent carbon atoms, thereby liberating hydrogen chloride and forming resins of the linear polymer type, when mixtures oi these compounds are heated, preferably under vacuum.

The organic phosphorus compounds considered suitable as starting materials may be arylphosphorus oxydihalides, alkylphosphorus oxydihalides, arylphosphorus suli'odihalide, alkylphosphorus suli'odihalide, arylphosphorus dihalides, alkylphosphorus dihalides, and similar compounds where the aryl or alkyl groups may contain substituted groups or radicals. Because of their availability, phenyl phosphorus oxydichloride, phenyl phosphorus sulfodichloride, and phenyl phosphorus dichloride are particularly the subject of this invention. 7

The hydroxy aromatic compounds which are suitable when chlorinated include such compounds as hydroquinone, resorcinol, dihydroxy naphthalenes, dihydroxy diphenyls, and the like, so long as the hydroxy radicals are attached to non-adjacent carbon atoms. All of these compounds will contain a chlorine substituted aryl group. Where the hydroxy radicals are on adjacent carbon atoms, their reaction with the phosphorus compounds gives a closed ring, deflnite type ester, whereas with non-adjacent hydroxy radicals there is no ring closure and the resulting product is a linear polymer.

The reaction for producing the linear type polymer may be illustrated by the following equation, showing the reaction of phenyl phosphorus oxydichloride and dichlorohydroquinone:

0 solution which became type reaction will take 2 Variations in the time, temperature, and pressure conditions affect the physical characteristics of the resin product.

Another typical reaction wherein the chlorinated hydroquinone is a tetrachlorohydroquinone is as follows:

I 0 Clean no 01 c1 c1 c1 0 o Mono and trichloro hydroquinones may likewise be reacted with a phosphorus dihalide compound to form linear polymers. The chlorine substituents on the hydroquinone may be attached to any of the four available carbon atoms. In the above reactions, the oxygen that is double bonded to the phosphorus atom may be replaced by sulfur.

It is believed readily apparent that the above place to form a linear polymer with any chlorinated dihydroxy aryl compound wherein the hydroxy radicals occupy non-adjacent carbon atoms. In all cases, the resulting polymer will contain repeating units of C1 Cl x -i -o-R-owhere R is a chlorine substituted arylene group and X is either oxygen or sulfur.

The following examples illustrate typical polymers and the methods 01' producing them.

Example I 41 grams (0.21 mole) of freshly distilled phenylphosphorus oxydichloride (CoHsPOClz) was added to 49.6 grams (0.2 mole) of tetrachlorohydroquinone (a buff-colored solid, M. P. 232-8 0., obtained from Eastman). The solid absorbed the liquid forming a hard cake. This was then heated under C0: to about C. when the reaction started and proceeded smoothly. The solid cake slowly liquefied to a dark colored a viscous black mass as 3 the time of heating and temperature increased. The heating conditions were as follows:

Temper- Time, hours Pressure agutij'e,

6 Atm- 170 16 Atm. 200 75 Atm. 220 4 1 mm- 190 20. 5 1 mm. 200 23 1 mm 236 24 1 mm. 270

The resin product was a hard, brittle. black solid having a melting point of 241 C. It was too brittle to be drawn into satisfactory fibers.

Example II The experiment was repeated under the 01- lowing temperature conditions:

Temper- Time, noun Pressure agige,

5 Atm. 100-200 11 Atm. 203 4. 5 Atm. 220 5. 1 mm. 230 16. 0 1 mm. 250 3. 0 1 mm. 280

The resin product was very similar to the above except its melting point was 232-234 C.

It is also possible to make copolymer resins where mixtures of dihydroxy aromatic compounds are employed. For example, phenylphosphorus oxydichloride may be condensed with a mixture of hydroquinone and tetrachlorohydroquinone to give a resin having a probable structure, where equal mole proportions are used, of

Example III Temper- Time, hum Premure etch-e,

4 Atm.- 130 18. Atm. 150 7. 5 Atm 100 23.0 Atm.- 180 23.0 2 mm-.. 200 l. 5 2 mm- 170 05.0 2 mm--- 200 5.0 2 mm--. 210 1.0 2 mm.-. 220

The product was a hard, translucent, black resin. It had a softening point of about 185 C. and a melting point of 197-210 C. It could be drawn into fibers of moderate strength.

Example W 37.2 grams (0.15 mole) of tetrachiorohydroquinone and 16.5 grams (0.15 mole) of hydroquinone were heated together with 64.4 grams (0.33 mole) of redistilled phenyl phosphorus oxydiohloride in an atmosphere 0! CO2 gas. The reaction proceeded smoothly at 13'0-140 C. with evolution of hydrogen chloride. The following heating conditions were employed:

Tempergg g Pressure a tuore,

1a Atm-.

a Atm 15.5 Atm- At this point a glass tube was submerged into the molten mass and CO: gas bubbled through the resin as the heating was continued as follows:

Temper- Ti Pressure agu'e,

4 Atm- 195 19 Atm 210 25 Atm 235 42 2 mm. 235

The resin product was a hard, translucent black solid, with a melting point of about -210 C. It could be drawn into long, fairly strong fibers having some cold drawing strength.

Example V 69.6 grams (0.33 mole) of phenylphosphorus sultodichloride, 37.2 grams (0.15 mole) of tetrachlorohydroquinone, and 16.5 grams (0.15 mole) hydroquinone were heated together, with 0.2 cc. of phenylphosphorus dichloride as a. catalyst. under a C02 atmosphere under the followin conditions:

Temper- Time, hours Pressure agie,

2 Atm. 130 15 Atm. 150 7 Atm- 190 70 Atm- 200 48 Aim. 232 18 1 mm... 232

The resin product was black and nearly opaque. It had a melting range or 1'70-180 0., but was too brittle to be drawn into satisfactory fibers.

Example VI 61.5 grams (0.315 mole) of freshly distilled phenyl phosphorus oxydichloride and 53.7 grams (0.3 mole) of purified dichlorohydroquinone 35 were heated under a CO: atmosphere. The heating was carried out under the following conditions:

Tempergg ig Pressure a tu e,

0. Atm 138 2. 75 Atm- 165 15.0 Atm 170 2. 5 Atm- 190 2.25 A1311... 210 2. 25 Atm 225 l Estimated.

Temperggig Pressure atlge,

15. 5 1'mm 165 3. 75 1 mm 190 4. 25 1 mm 205 87. 75 1 mm. 225

The product was a hard, tough resin with a melting point of mil-186 C. It was somewhat rubbery at its melting point and could be drawn into fairly strong fibers.

From the above examples, it is readily seen that a large number of phosphorus-containing linear type polymers can be made depending upon the reaction and polymerizing conditions employed. These resins have utility in the production of artificial fibers, lacquer coatings, mold compositions, laminated glass, plasticizers for cellulose plastics, lubricating additives, fire retardent additives in inflammable plastics and the like.

The foregoing detailed description has been given for clearness of understanding only and no unnecessary limitations should be understood therefrom.

I claim:

1. A fusible linear polymer in which the repeating units consist of I wherein R is an aromatic nucleus containing only chlorine substituents with said oxygen linkages being only on non-adjacent carbon atoms of the aromatic'nucleus and X is a member of the class consisting of oxygen and sulfur.

2. The polymer of claim 1 wherein X is oxygen.

3. The polymer of claim 1 wherein X is sulfur.

4. The polymer of claim 1 wherein R is a dichloro phenylene group.

5. The polymer of claim 1 wherein R is a tetrachloro phenylene group.

6. The polymer of claim 1 wherein the repeating unit is 7. The polymer of claim 1 wherein the repeatins unit is 0 Cl Cl 4L0 o- 8. The method of producing phosphorus-containing resins which comprises heating a phosphorus compound having the formula RPYCI: and a dihydroxy compound having the formula HOR'OH wherein R is an aryl nucleus. Y is a member of the class consisting of oxygen and sulfur, R is a chlorinated arylene nucleus containing only chlorine substituents, and the OH groups are on non-adjacent carbon atoms, the heating being carried out initially at a temperature sufllcient to cause condensation with liberation of hydrogen chloride, then under reduced pressure at a temperature and period of time sufficient to effect a high degree of polymerization, said phosphorus compound and said dihydroxy compound being employed in substantially equal molecular proportions.

9. A fusible linear polymer of the class consisting of polymers containing only the repeating unit:

and

wherein X is a member of the class consisting of sulfur and oxygen, R is a chlorinated arowherein x is a member of the class consisting of sulfur and oxygen, R. is a chlorinated aromatic nucleus containing only chlorine substituents, and R. is an unsubstituted aromatic nucleus,

7 each or said units having the oxygen linkages on nonadjacent carbon atoms of the corresponding aromatic nucleus.

11. The polymer of claim 10 wherein R is a dichloro phenylene group and R is a phenylene group.

12. The polymer of claim 10 wherein R is a tetrachloro phenylene group and R is a phenylene group.

13. The method of producing phosphoruscontaining resins which comprises heating phenyl phosphorus oxydichloride and a dihydroxy compound having the formula HOR'OH wherein R is a chlorinated arylene nucleus containing only chlorine substitutents and the OH groups are on non-adjacent carbon atoms, the heatin being carried out initially at a temperature suflicient to cause condensation with liberation of hydrogen chloride, then under reduced pressure at a temperature and period of time sufllcient to effect a high degree of polymerization, said phosphorus compound and said dihydroxy compound being employed in substantially equal molecular proportions.

14. The method of producing phosphoruseontaining resins which comprises heating a phosphorus compound having the formula RPYCh wherein R is an aryl nucleus and Y is a member or the class consisting of oxygen and sulfur with dichlorohydroquinone, the heating being carried out initially at a temperature sumcient to cause condensation with liberation of hydrogen chloride then under reduced pressure at a temperature and period of time suflicient to efiect a high degree of polymerization, said phosphorus compound and said dichlorohydroquinone being employed in substantially equal molecular proportions.

15. The method of producing phosphoruscontaining resins which comprises heating a phosphorus compound having the formula RPYCI: wherein R is an aryl nucleus and Y is a member of the class consisting of oxygen and sulfur with tetrachlorohydroquinone, the heating being carried out initially at a temperature sumcient to cause condensation with liberation of hydrogen chloride, then under reduced pressure at a temperature and period of time sumcient to efiect a high degree of polymerization, said phosphorus compound and said tetrachlorohydroquinone being employed in substantially equal molecular proportions. a

ARTHUR DOCK FON TOY.

No references cited. 

1. A FUSIBLE LINEAR POLYMER IN WHICH THE REPEATING UNITS CONSISTS OF 